Step-wise process for coloring anb fin-
ishing cellulose materials wherein a
cationic dye-fixing agent is employed
with the resin finishing agent



United States Patent 3,193,595 STEP-WISE PRUCESS FOR CQLGRING AND FEN-ISHHNG CELLULQSE MATEREALS WHEREHN A (ZATIONIC DYE-FDHNG AGENT ISEMPLGYED WITH THE RESTN FTNL SHENG AGENT Jack Frauhland Mawson, IanDurham Rattee, and Erwin Seltzer, Manchester, England, assignors toImperial Chemical Industries Limited, London, England, a corporation ofGreat Britain No Drawing. Filed May 3, 1962, Ser. No. 192,063 Claimspriority, application Great Britain, May It}, 1961, 17 ,titlti/ 61 9(Ilaims. (Cl. 8-48} This invention relates to a new colouration process.More particularly, the invention relates to a process for the finishingof cellulose textile fabrics coloured with reactive dyestuffs whereby avery high level of fixation of: dyestufi" on the fibre is combined withexcellent quality of dyeing.

It is well known to dye or print cellulose textile fabrics with reactivedyestufis, and thereafter to submit the fabric to a conventionalfinishing treatment to obtain a creaseresistant or dimensionallystabilised coloured fabric. It has now been found that in such aprocess, a valuable eifect may be obtained by adding a cationicdye-fixing agent to the liquor from which the resin-finishing agent isapplied. This procedure prevents unfixed dyestutr" from dissolving inthe resin-finishing bath, and assists fixation so that the expensive andtime-consuming washing process normally required when dyeing withreactive dyestuffs can be dispensed with between the dyeing andfinishing steps, and is considerably shortened and frequently may bedispensed with entirely after the resin-curing step.

By a cationic dye-fixing agent, we mean an organic compound free fromanionic water-solubilising groups such as sulphonic acid groups, butcontaining one or more ammonium groups, and frequently, but not always,an aliphatic chain of 6 or more carbon atoms. As examples of suchcompounds there may be mentioned the following classes:

(a) Compounds having an ammonium group and at least one aliphatic orcycloaliphatic residue having at least carbon atoms. Such substances arenamed in United Kingdom specifications Nos. 339,962, 366,918, 441,767,443,588, 646,921 and 496,611. These substances may be applied inconjunction with a copper salt as described in United Kingdomspecification No. 535,582.

(b) The condensation products of formaldehyde with dicyandiamide, ormixtures of urea and dicyandiamide in the presence of amine or ammoniumsalts. Such products are described in United Kingdom specifications Nos.19783/38, 576,562 and 651,139. These products may also be applied inconjunction with a copper salt.

(c) The condensation products of aldehydes with hydroxyalkyl derivativesof amino and imino compounds, in the presence of salts of nitrogencontaining inorganic or organic bases. Such products are described inUnited Kingdom specification No. 611,235.

(d) The water-soluble condensation products of nitrogen-containingcomplex copper compounds with compounds containing at least once thegrouping:

and with aldehydes of low molecular Weight. Such prod nets are describedand claimed in United Kingdom specification No. 736,792. 7

(e) The acid salts of the condensates of cyanamide, di-

cyandiamide N-substituted dicyandiamides, guanidine and Patented Aug..3, 1965 N-substituted guanidines, with polyalkyleneimines. Suchproducts are described and claimed in United Kingdom specifications Nos.522,539, 657,753, 755,478 and 755,519.

(f) Arylene and alkylene biguanides such as those described and claimedin United Kingdom specification No. 705,833 and their polymers.

('3) The quaternary salts of polyaminoethylacrylates and otherpolymerised ethylenically unsaturated compounds containing primary,secondary or tertiary amino groups.

Thus according to the present invention there is provided theimprovement in the process of colouring textile materials consistingwholly or partly of fibrous cellulose by application of a reactivedyestuff, thereafter applying a resin-finishing agent and thereafterbaking the treated material to cure the resin, which improvementconsists of adding to the aqueous liquor containing the resinfinishingagent, a cationic dye fixing agent as hereinbeiore defined.

By a reactive dyestuft we mean a water-soluble dyestun which contains areactive halogen atom or other substituent capable of reacting with theresin or fibre so that the remainder of the dyestuff becomes attached tothe resin or fibre through a covalent bond. As examples of suchdyestuffs, there may be mentioned, for example, dyestufis containings-triazinyl or pyrimidyl radicals carrying labile atoms or groupsdirectly attached to the ring, and dyestuffs containing abeta-halogenopropionyl, betahalogenoethylsulphonyl, betahalogenoethylsulphamyl, beta-sulphatoethylsulphonyl, betahydroxyethylsulphonyl, chloro-acetylamino,beta-(chloromethyl)-beta-sulphatoethylsulphamyl, acryloylamino,beta-(alkyland aryl-sulphonyloxy) alkyl sulphonyl,beta-acyloxyalkylsulphonyl, vinylsulphonyl, alkyl phosphite or sulphonfluoride radical.

By a labile atom or group, We means an atom or group which is bound by acovalent bond to a carbon atom of the pyrinn'dine or triazine nucleusbut which readily dissociates under the influence of heat or alkalis,especially in the presence of moisture, to form an ion or an unchargedmolecule. As examples of such atoms or groups, there may be mentioned,for example, bromine, or, preferably, chlorine atoms, sulphonic acidgroups, thiocyano groups, negatively substituted aryloxy and arylthiogroups, such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy,disulphophenoxy and sulphonaphthoxy groups, quaternary ammonium groups,groups of the formula:

Y r I wherein Y represents the group of atoms necessary to form a 5- or6-membered heterocyclic ring which may carry substituents or form partof a fused ring system;

groups of the formula:

wherein R and R each represents the same or different aikyl, cycloalkyl,aryl or aralkyl groups, or R and R together form, together with thenitrogen atom, a 5- or 6-membered heterocyclic ring; and groups of theformula:

contain metal in complex formation. Specific examples of suitabledyestuffs are described in United Kingdom specification No. 209,723 inExamples 1 and 2, United Kingdom specification No. 298,494 in Example 1,in United Kingdom specifications Nos. 460,224, 733,471, 740,533,775,308, 772,030, 774,925, 780,591, 781,930, 785,120, 785,222, 802,198,805,562, 826,689 and 852,604, and 937,182 and 924,990.

There may also be used dyestuffs containing hydroxyl, amino,hydroxyalkylamino, guanyl hydrazide, semicarbazide r thiosemicarbazidegroups linked to a triazine nucleus or hydroxyalkylamino groups linkedto a pyrimidine nucleus or to the alkyl radical of an alkylsulphonyl,alkylsulphamyl, alkylcarbonyl or alkylcarbonamide group. Dyestuffs ofthese types have been described, for example in United Kingdomspecification No. 209,723 in Example 1, in United States Patent No.2,768,158 and United Kingdom specifications 904,227,

929,425 and 927,404, and the use of dyestuffs of these types has beendescribed, for example in French Patents Nos. 1,206,833 and 1,208,532.

The dyestuif is applied to the textile material by immersion of thematerial in an aqueous solution of the dyestulf preferably by padding orby application of a printing paste containing .the dyestuif. Theprinting paste may be applied by any of the usual methods, such as byroller, block, screen or stencil. The dyestuff solution may containother additions commonly used in the .art of dyeing with reactivedyestuffs, for example, urea,

wetting agents, such as alkali metal alkylated naphthalene sulphonatesand condensates of ethylene oxide with alkylated phenols, fatty alcoholsor fatty amines, migration inhibitor such as sodium chloride, sodiumsulphate or sodium alginate and, usually, an acid binding agent to aidreaction with the fabric. The acid-binding agent is only necessary toachieve reaction with the fabric, and where the dyestuff is capable ofreaction with the resin, there is no need to use an acid-binding agent.It is preferred to use a mild alkali, such as sodium carbonate orbicarbonate, as the acid-binding agent to minimise neutralisation of anyacid or acid salt which may be used as curing catalyst in the subsequentprocessing.

After application of the dyestulf solution, the fabric is preferablydried at atmospheric temperature, but may also be dried at elevatedtemperatures for example by .treating with hot air at a temperature ofbetween 50 to 150 C. or by treatment with steam in a steamer at atemperature of 100 to 105 C. for about 2 to 20 minutes. Before drying,fabric which has been dyed, particularly when containing viscose rayon,is advantageously allowed to stand in a moist condition for a period oftime, which may be from minutes to 24 hours, preferably from 30 minutesto 2 hours, the treatment leading to improved fixation and diffusion ofthe dyestuif into the fibres, and hence to improved quality andappearance of dyeing.

The printing pastes containing the dyestulf may also contain theadditives usually used with reactive dyestuffs such as urea, sodium,m-nitro-benzene sulphonate, wetting agents of the types indicated aboveand thickening agents such as sodium alginate, ethyl cellulose, starch,locust bean gum, and, preferably, oil-in-water emulsions andwater-in-oil emulsions.

After application of the printing paste, the fabric is preferably dried,for example by passage over heated rollers, and may, if desired, then bebaked or steamed for, for example, from 2 to minutes.

The dried textile fabric is then treated with the resinfinishing agent,for example by padding the material through an aqueous solution orsuspension of the agent. The solution or suspension may contain othercommonly-used additives for example curing-catalysts for for about 1minute.

4: the resin-finishing agent, which may be acidic or alkaline asnecessary, anionic and nonionic surface active agents, lubricatingagents, softening agents, water repellentsand stiffening or bodyingagents, as well as the cationic dyefixing agents.

As examples of resin-finishing agents which may be used, there may bementioned acetal cellulose reactants (as defined in the TextileResearch. Journal for 1959 at page 74) and, more particularly, mixturescomprising the methylol derivatives or lower alkyl ethers of methylolderivatives of monomeric or polymeric compounds containing a pluralityof amino or mono substituted amino groups, said compounds being knownfrom the art or used in practice for the formation of resins bycondensation with formaldehyde. Suitable compounds include, for examplemonomeric nitrogen compounds such as urea, thiourea, substituted ureasand thioureas, dicyandiamide, dicyandiarnidine, biguanides, amides,carbamates, allophanates and heterocyclic compounds such asaminotriazines, urons, ureins, ureides, imidazolidones, triazones andhydantoins or mixtures of such compounds, and polymeric nitrogencompounds such as the polymeric amides made by the reaction of dibasicacids with diamines. The lower alkyl ethers of the methylol derivativesof these compounds include for example the methyl, ethyl, propyl andbutyl ethers. Other resin-finishing agents which may be used arecondensation products of ketones with aldehydes, in particular, CI-I O.

As examples of acid catalysts which may be used there may be mentionedsalts formed from weakbases and mineral acids such as zinc chloride,ammonium sulphate and ammonium chloride, mineral acid salts of organicamines, weak acids, for example organic acids such as oxalic acids andsubstantially neutral substances which develop acidity on heating orsteaming, such as magnesiumchloride and ammonium thiocyanate; mixturesof such catalysts may be used.

As examples of alkaline catalyst which may be used there may bementioned sodium bicarbonate and sodium carbonate.

The aqueous solution used for application of the resinformingcomposition may contain between 3% and 40% and preferably between 5% and30% of the resin-forming compositionsand between 0.1% and 5% andpreferably between 0.5% and 3.0% of acid or alkali catalyst.

As examples of lubricating and softening agents which may be used, theremay be mentioned, for example dispersions of natural or synthetic waxes,methylol stearamide and the quaternary ammonium salts of United Kingdomspecification No. 808,265 (which in low concentration act as lubricantsrather than as cationic dye-fixing agents). The amount of dye-fixingagent used can vary within wide limits, in some cases as little as 0.005gram per litre of padding liquor being effective whilst in other casesas much as 1.5 grams per litre is required. These amounts are those atwhich a reasonable effect is shown and the use of higher quantities upto to grams per litre will give improved results.

The baking stage may be carried out at a wide range of temperatures,provided the temperature is sufficiently high to cure the resin. Thetimesof baking will depend upon the temperature used, a short period ofheating, for example, about 10 seconds, being suificient at temperaturesof the order of 200 C. whilst a period of about 1 to 5, usually 3,minutes is required at a temperature of about 155 C. The bakingtemperatures are preferably maintained at between C. and 200 C.adjusting the time to minimise thermal degradation of the cellulose.

If desired, the textile material can be given a short washing treatment,for example, a treatment in a weakly alkaline aqueous solution of soapor detergent at the 'boil This washing treatment serves the purpose ofremoving small amounts of unpolymerised resin-forming agent and theresidual acidity caused by the acid catalyst or the decompositionproducts thereof.

The invention is illustrated but not limited by the following examplesin which parts and percentages are by weight:

Example 1 100 parts of viscose rayon fabric are padded with a solutioncontaining parts of the copper complex of 2- (5'sulpho-2'-hydroxyphenylazo)-6-(2",4"-dichloro-6"-s-triazinylamino)1-naphthol-3,S-disulphonic acid, 10 parts of sodiumbicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate in975 parts of Water, squeezed, maintained in a moist condition atatmospheric temperature for 1 hour and dried at 70 C. in a hot airdrier.

The fabric is then padded through 1000 parts of a solution containing400 parts of a 60% aqueous solution of a urea-formaldehyde precondensate(obtained by stirring a mixture of 1 mole of urea and 1.6 moles offormaldehyde at pH 8.5 and 20 C. for 4 /2 hours), parts of ammoniumdihydrogen phosphate, parts of the condensate of dicyandiamide,formaldehyde and ammonium chloride obtained as described in Recipe 1 ofUnited United Kingdom specification No. 808,265. The fabric 1 is thensqueezed, dried on a pin stenter at 100 C. and baked at 150 C. for 3minutes. The fabric is dyed a bluish-red shade having good fastness tosevere Washing treatments and is resistant to creasing.

The following table sumrnc rises further examples of the new process,following the procedure of Example 1 above, but substituting thedyestufi' named in the first column for that used in the first paddingsolution and using the resinfinishing agent, acid catalyst and cationicdye-fixing agents named in the second, third and fourth columns for theurea-formaldehyde precondensate, the ammonium dihydrogen phosphate andthe dicyandiamide/formaldehyde/ ammonium chloride condensation product,respectively.

In each case a fabric is obtained-having excellent fastness to creasingand coloured in the shade described in the fifth column; the dyeing hasgood fastness to severe washing:

Dyestufi Resin-finishing agent Acid catalyst Cationic dyte-fixing Shadeagen 2. Disodium i-amino t-(3--sulphatoethylsulphonylaniline) an- As inExample 1- As in Example 1 As in Example 1. Brightredthraquinone-2-sulphonate, 5 parts. dish-blue.

3. The dyestufi having the formula: do ..do d0 Bright-red,

SI 0 H H g 503E (1)11 l IIHC\ N N N=N- C1 H0 38 s 0 3H 10 parts 7 4.1-(2,5-dichloro-4-sulphophenyl)-3-methyl-4-(5-diehloro-s- 70% aqueoussolu- Dicthanolamine 1,4-phenylene bigua-Greenishtriazinylamino-2-sulphophenylazo)-5-pyrazolone, parts. tionof1,3-d1- hydrochloride mde hydroyellow.

methylol-2- 10 parts. chloride, 10 parts. imidazolidone, 80 parts.

5. 6-(N-dichloro-s-triazinyl-N-methyl)amjno-1-hydroxy-2,2- As in Example4- Magnesium chlo- 1,6-hexamethylene Orange.

azonaphthalene-l,3,5-trisulphonic acid, 10 parts. ride, 12 parts.higuazrde p501 mer, par s.

6. l-(dichloro-s-triazinyl) amino-7-phenylazo-8-naphthol-3,6- 50%aqueous solu- Magnesium chlo- Cetyl pyricliuium Bluish-red.

disulphonic acid, 5 parts. tion of hexamethride, 15 parts. bromide, 20parts.

oxymethylmelamine, 70 parts. 7 7. l-amino-t[-(dichlorostriazinyl) aminoanilinolanthraquinone- 50% aqueous solu- Ammonium dihy- The polymer ofthe Greem'sh. 2,3,5-trisulphonic acid, 10 parts. tion of 4,5-d1hydrogenphosphate, dimethyl sulphate blue.

droxy-LBJneth- 10 parts. quaternary amylo1-2-imidazmonium salt ofoliclone, 70 parts. diethylaminoethyl methacrylate, 10 parts.

8. The copper complex of 6-(dichloros-triazinyl)tuninO-Z-W- 45% aqueoussolu- Magnesium chlo- Saturated aqueous Da b1(2,5-disulphophenylazo)-5-mcthyl-2-hydroxyphenylazo]- tion oftrimethride, 6 parts; solution or chloro- 1-naphthol-3,5-disulphonicacid, 20 parts. ylol urea, 60 tartaric acid, 1.4 hexidine hydroparts.parts. chloride, parts.

9, 1-amino-4-[4"-(dichloros-triazinyl)amino-2,2-disulphostilben- 60%aqueous solu- Diethanolam ne 1,6-l1examethylene Gr4-y1amino]anthraquinone-2,5-disulphonic acid, 10 parts. tion of a 1:1.6fhydrochloride, 10 biguamde po1yurea/formaldeparts. mar, 25 parts. hydecondensate, 300 parts. p

10. The 1:2-chromium complex of G-(dichloro-s-triazinyl)amino- 50%aqueous solu- Ammonium dihy- 1,4-phenylene bigua- Reddish. 2-(2'-carboxyphenylazo)-1-naphthol-3-sulphonic acid, 10 parts. tion ofhexamethdrogen phosphate, nide polymer, b

oxy-methyl mel- 15 parts. 20 parts. amine 70 parts.

11. The copper complex of 8-(2-amiuo-4-chloro-s-triazinyl)aminoaque us SZ1110 trate, 10 As in Example 1-.-- Royal blue.

1,1 dihydro1;y-2,2-azo-naphthaoene-3,-6,8-tetrasulphonic tion oftnparts. acid, 10 parts. :grgethyllol urea,

par s.

12. The copper complex of 8-(2-m-sulphoanilinoy-chloros-triaqueous solu-Magnesium chlo- Cetyl pyridinium Purple.

azinyl)amin0-2-(3-chloro-5-sulpho-2-hydroxyphenylazo)- tion of4,5-d1hyride, 12 parts. bromide. 1-naphth0l-3,6-disulphonic acid, 15parts. droxy-1,3-d1- methylol-Z-imldazolidone, 80 parts. 13.1-(2-chlor0-6-methyl-4-sulphophenyl)-3-methyl i-(2-methoxy- 70% aqueoussolu- Zinc nitrate, 10 The condensate of Greenish-5',8-sulphatocthylsulphonylpheuylazo)-5-pyrazolone, 10 parts. tion ,3-d1- parts; tartaric ethylene bis-diye110w methylol-2-1m1dacid, 1 part.cyandiamide with azolidone, 80 diethanolamine parts. hydrochloride,

parts.

14. The copper complex of 1-(4-sulphophenyl)-3-methyl-4-(2'- 50% aqueoussolu- Diethanolemine Saturated aqueousRcddishhydroxy-5-B-sulphatocthylsulphonylphenylazo)5-pyrazolone, tion ofhexahydrochloride, solution of chloroyellow. 15 parts. methoxymethyl- 7parts; ammohexidme hydromelamine, nium nitrate, chloride, 30 parts.parts. 3 parts.

Dyestuft Resin-finishing agent Acid catalyst Cationic dyte-fixing Shadeagen 15. 2-(2-methoxy-5-fi-sulphatocthylsulphonylphenylazo)-1- As inExample 1 Zinc nitrate, 10 As in Example 1 Red.

naphthol-S-sulphonic acid, 10 parts. parts. 16. The copper complex ofS-acetylamin-2-(2-hydroxy-5-;3- 45% aqueous solu- Ammonium di-1,6-hexamethylcne Violet.

sulphatoethylsulphonylphcnylazo)-1-naphthol-3,G-disulphonic tion 0trihydrogen phosbiguanide polyacid parts. methylol urea, 40 photo,parts. nier, parts.

parts; 50% aqueous solution of hexamethoxy mcthylrnclamine, 40 parts.

Example 17 In this example, the procedure followed is that of Example 1,with the exception that the sodium bicarbonate is omitted from the firstpadding solution.

The coloured fabric so obtained has a lower fastness to severe Washingtreatments, but has a commercially satisfactory standard of fastness tothe mild washing treatments normally recommended for viscose rayonfabrics.

The following table lists dyestuffs which can be used in the aboveprocedure in place of these named in Example 1. The second paddingliquor can be formulated in accordance with any of those described inExamples 1 to 16 inclusive.

Example Dycstutf Shade 18 The product obtained by condensing copperTurquoise. phthaloeyaniue tetra- (3')- sulphonchloride with 1.5 moles ofB-chloroethylaminc in the presence of ammonia.

The product. obtained by condensing copper phthalocyanine tri- (3)-sulphonchloride mouosulphonic acid with 1.5 moles of 5 ehloroethylamine.

The product obtained by condensing copper phthalocyanine tri- (3)-sulphonchloridc monosulplionic acid with one mole of pphenylene diaminesulphonic acid in the presence of ammonia and reacting with 1 mole of2,4,6-trichloropyrimidine.

The 1:2-chroniium complex of 6- -1nethoxy-4-chlor0-s-triazinylamino)-2-(2-carb0xypl1enylazo)-1-naphthol-8snlphonicacid.

A mixture of 1 part of the lz2-cobalt and 3 parts of the l:2-chromiumcomplex of 6- "1Ini110-4-chloro-s-triazinylamino)-0-nitro-1,2-dihydreary-2,1,-azonaphthalcne-SA -di s l p h o n i c act The copper complex of 6-(2-m-sulphoanilino- 4,-ch1oros-triazinylamino) 2-[4-(2,5-d is u lphophenylazo)-5"-mcthyl-2"-hydroxyphenylazo}1-3,fi-disulphonic acid.

The product obtained by condensing copper phthalocyanine tri- (3-snlphonchloride monosulphonio acid with 1 mole oi2-a1nino4-ehloro-6-(4-amino-3-sulphaoanilino)-s-triacme.

8- [2, 4,-di (hydroxynicthylamino)-s-triazin-6- ylamino]-2- (2-sulphophenylazo) -1-naphthol3,5-disulphonic acid.

S-[2, 4'-di (pcntahydroxyn-hexylamino)stri azin-G-ylami11o]-2- (2-sulphophc11ylar.0)-lnaphthol 3,G-disulphonic acid.

Reddishbrown.

22 Dark grey.

23 Dark blue.

24 Turquoise.

Grecnishyellow.

Bright red.

Example 28 chloride obtained as described in Recipe 1 of United King--dom specification No. 651139, 1.15 parts of aqueous ammonia of specificgravity 0.88, 5 parts of a 50% aqueous dispersion of methylolstearamide, 1 part of the product obtained by condensing cetyl alcoholwith 17 moles of The fabric is then squeezed, dried on a stenter at C.

and baked at 150 C. for 5 minutes.

The fabric is then washed at 100 C. for 1 minute with a solutioncontining 3 parts of sodium carbonate and 1 part of the reaction productof octyl phenol with 8 moles of ethylene oxide per 1000 parts water,rinsed and dried. The fabric is dyed a greenish-blue shade which is fastto severe washing treatments and resistant to creasing.

if in the above example the'dyestuff is replaced by 10 parts of theproduct obtained by condensing 1 mole of tetrachloropyrimidine with3-rnethyl-1-(2,5-dichloro-4'- sulphophenyl) 4(5"-amino-2-sulphophenylazo)-5- pyrazolone, the fabric is dyed a fastgreenish-yellow shade and is resistant to creasing.

Example 29 A printing paste containing:

Parts Dyestuff of Example 1 of specification No. 846,949 2 later 32Oil-in-water emulsion thickening 55 Sodium alginate thickening (4%sodium alginate) 9 Sodium m-nitrobenaenesulphonate 1 Sodium bicarbonate1 is printed on mercerised cotton fabric and the fabric is dried at 70C. and then treated for 5 minutes with steam at atmospheric pressure.

The printed fabric is then padded in the resin pad liquor described inExample 28, dried and heat baked for 3 minutes at 150 C. The fabric isthen washed as described in Example 28 and finally dried.

A bluish-red print is obtained on the cotton which possesses goodfastness to' light and washing and which is resistant to creasing.

The emulsion thickening used in the above example may be obtained byadding 80 parts of white spirit to a rapidly stirred mixture of 5 partsof a 26.5% aqueous solution of the condensate of octyl phenol with 8moles of ethylene oxide, 7 /2 parts of a 20% aqueous solution of thecondensate of cetyl alcohol with 17 moles of ehtylene oxide, and 7 /2parts of water.

Example 30 In place of the dyestuif used in Example 29 there are used 2parts of the dyestuif of Example 2 of specification No. 83 8,335 and theresultant printing paste is printed on viscose rayon. The fabric isdried at 70 C. and then heat treated for 3 minutes at C.

The printed fabric is then padded in the resin pad liquor described inExample 1 and heat treated for 3 minutes at C. The fabric is then washedas described in Example 28, rinsed in water and finally dried.

A bright reddish-blue print is obtained on the viscose fabric possessinggood fastness to light and washing and which is similar in strength toan unsoaped print produced by the same method.

Example 31 100 parts of a mercerised cotton poplin fabric are paddedwith a solution containing 5 parts of the copper complex of the compoundof the formula:

10 parts of sodium bicarbonate and 5 parts of sodium triisopropylnaphthalene sulphonate in 980 parts of water, squeezed, dried at 70 C.in a hot air drier and baked for 3 minutes at 150 C. The fabric is thenpadded through an aqueous solution containing 80 parts of a 40% aqueoussolution of 1,3-dimethylol-5-beta-hydroxyethyl-hexahydro-triazin-Z-one,10 parts of zinc nitrate hexahydrate, 10 parts of hexarnethyleuebiguanide polymer, 5 parts of a 50% aqueous dispersion of methylolstearamide, 1 part of the product obtained by condensing cetyl alcoholwith 17 moles of ethylene oxide and 1 part 05 acetic acid in each 1000parts. Thefabric is then squeezed, dried on a stenter at 100 C. andbaked at 150 C. for 5 minutes. The fabric is then washed at 80 C. for 1minute with a solution containing 3 parts of sodium carbonate and 1 partof the reaction product of octyl phenol with 3 moles of ethylene oxideper 1000 parts of Water, rinsed and dried. The fabric is dyed a purpleshade which is fast to severe washing treatments and the fabric isresistant to creasing.

If the dyestuff used in the above example is replaced by 10 parts of thedyestuif of the formula:

SIOQH II I I son II I N O NH SOaH the material is dyed a fast blue shadeand is resistant to creasing.

Example 32 Example 33 100 parts of bleached mercerised plain weavecotton fabric are padded, at 100% expression, with a solutioncontaining, per 1000 parts, 10 parts of the copper complex of6-(dichloro-s-triazinylamino)-2-[4'-(2",5"- disulphophenylazo) methyl 2'hydroxyphenylazo1- l-naphthol-3,5-disulphonic acid, parts of sodiumbicarbonate, 5 parts of sodium triisopropyl naphthalene sulphonate andis then dried in warm air at 70 C. The fabric is then padded, at 100%expression, through a solution containing, per 1000 parts, 200 parts ofa 60% urea-formaldehyde precondensate, 30 parts of sodium bicarbonate,62 parts of the condensation product of ethylene bisdicyandiamide anddiethylene triarnine hydrochloride, 5 parts of a 50% aqueous dispersionof methylol stearamide and 1 part of the condensation product of cetylalcohol with 17 moles of ethylene oxide. It is then dried in warm air at70 C. and baked for 3 minutes at sulphonate.

. 10 160 C. The fabric is then washed off as described in Exarnple 28.

The fabric is then dried to a dark blue shade, which is fast to washing,and is resistant to creasing.

Example 34 100 parts of bleached mercerised botton poplin are paddedwith a solution containing 28 parts of the 1:2-chromium complex and 12parts of the 1:2-cobalt complex of 1(4'chloro-6-amino-s-triazine-2'-ylarnino)- 2 (5"- nitro -2-bydroxyphenylazo) 8 naphthol 3,6- disulpnonic acid, 5 parts of sodiumtriisopropyl naphthalene sulphonate and 10 parts of sodium bicarbonatein 100-!) parts of water, squeezed to 100% expression, maintained in amoist condition for 45 minutes at atmospheric temperature and dried. Thefabric is then padded through a solution containing parts of a 40%aqueous solution of l,3-dimethylol-5-fi-hydroxyethylhexahydrotriazin-Z-one, 6.5 parts of magnesium chloride hexahydrate, 2 parts of tartaricacid, 5 parts of a 50% aqueous dispersion of methylolstearamide, 1 partof the product obtained by condensing cetyl alcohol with 17 moles ofethylene oxide and 20 parts of the condensate of dicyandiamide,formaldehyde and ammonium chloride obtained as described in Recipe 1 ofUnited Kingdom specification No. 651,139.

Example 35 A viscose rayon fabric is padded at expression with asolution containing, per 1000 parts, 10 parts of 4-[5"-(dichloro-s-triazinylamino)-3"-sulphophenylazo] 1-(4'-sulph-ophenyl)-3-carboxypyrazolone, 10 parts of so dium bicarbonateand 5 parts of sodium triisopropyl naphthalene sulphonate, and dried at70 C.

The dried fabric is then subjected to the treatment described in thesecond paragraph of Example 1. It is dyed a reddish yellow shade havinggood fastness to mild washing treatments and is resistant to creasing.

Example 36 A viscose rayon fabric is padded at 100% expression with asolution containing, per 1000 puts, 10 parts of 1- =amino-4-[4'-dichloro-s triazinyla-minoanilino]anthraquinone-2,3',5-trisulphonicacid and 5 parts of sodium butyl naphthalene sulphon-ate, and is thendried at 70 C.

The fabric is then subjected to the treatment described in the secondparagraph of Example 1. It is dyed a greenish blue shade fast to mildwashing treatments and is resistant to creasing.

Example 37 100 parts of a mercerised cotton poplin fabric are padded at100% expression with a solution containing 10 parts of la-mino4-(3-dichloro-s-triazinyl-aminoanilino) anthraquinone-2,4-disulphonic:acid, 10 par-ts of sodium bicarbonate and 5 parts of sodiumtriisopropylnaphthalene It is .then dried at 70 C. and baked for 3minutes at C.

The fabric is then subjected to the treatment described in the secondparagraph of Example 28. It is dyed a reddish-blue shade which is fastto severe Washing treatments and resistant to creasing.

What We claim is:

1. In the process of colouring cellulose materials comprising treatmentwith a reactive dye-stuff, thereafter applying a resin-finishing agentand thereafter baking the treated material to cure the resin, theimprovement which consists in adding to the aqueous liquor containingthe resin-finishing agent, an organic cationic dye-fixing agent freefrom anionic solubilizing groups and having at least one ammonium group.

2. Process according to claim 1 consisting essentially in the followingsequence of steps:

(a) the textile material is immersed in an aqueous solution of thedyestutf containing an acid-binding agent,

(b) the fabric is thereafter maintained in a moist condition atatmospheric temperature for a period of time of from 15 minutes to 24hours and is then dried,

() without any intermediate washing step, the material is treated withthe liquor containing the resin-finish ing agent and said cationic dyefixing agent, and

(d) the material is thereafter baked to cure the resin.

3. Process according to claim 1 consisting essentially in the followingsteps:

(a) the textile material is immersed in an aqueous solution of thedyestuff which is free from acidbinding agent,

(b) the fabric is thereafter maintained in a moist condition atatmospheric temperature for a period of time of from minutes to 24 hoursand is then dried,

(c) without any intermediate washing step, the material is treated withthe liquor containing the resin-finis ing agent and said cationic dyefixing agent, and

(d) the material is thereafter baked to cure the resin.

4. Process =accordingto claim 1 consisting essentially in the followingsequence of steps:

(a) the textile material is immersed in an aqueous solution of thedyestuif containing an acid-binding agent,

(b) the material is dried,

(c) without any intermediate washing step, the material is treated withthe liquor containing the resinfini-shing agent and cationic dye fixingagent, and

(d) the material is thereafter baked to cure the resin.

5. Process according to claim 1 consisting essentially in the followingsteps:

(a) the textile material is immersed in an aqueous solution of thedyestuff which is free from acid-binding agent,

(b) the material is dried,

(0) without any intermediate washing step, the material is treated withthe liquor containing the resinfinishing agent and cationic dye fixingagent, and

(d) the material is thereafter baked to cure the resin.

6. Process according to claim 1 consisting essentially in the followingsequence of steps:

(a) the textile material is immersed in an aqueous solution of thedyestuif containing an acid-binding agent,

(b) the material is dried and subjected to a baking step,

(c) without any intermediate Washing step, the mate 12 rial is treatedwith the liquor containing the resinfinishing agent and cationic dyefixing agent, and

(d) the material is thereafter baked to cure the resin.

7. Process according to claim 1 consisting essentially in the followingsequence of steps:

(a) the textile material is immersed in an aqueous solution of thedyestuff containing an acid-binding agent,

(b) the fabric is thereafter maintained in .a moist condition atatmospheric temperature for a period of time 'of from 15 minutes to 24hours and is then dried,

(c) the textile material is then subjected to a baking step,

(d) without any intermediate washing step, the material is treated withthe liquor containing the resinfinishing agent and cationic dye fixingagent, and

(e) the material is thereafter baked to cure the resin.

8. Process according to claim 1 characterised in that the textilematerial after treatment is then subjected to a Washing step to removeunpolymerised resin-formin g agent and residual acid, and is dried.

9. Process according to claim 1 characterised in that a linen textilematerial treated, and thereafiter it is subjected to a mercerisationstep and washed to remove alkali and is dried.

References Cited by the Examiner UNITED STATES PATENTS 2,768,158 10/56Strobel et a1. 81.2 3,116,103 12/63 Gamlen et a1. 8-18 FOREIGN PATENTS209,723 3/25 Great Britain.

496,611 12/38 Great Britain.

535,592 4/41 Great Britain.

611,235 10/ 48 Great Britain.

651,139 3/51 Great Britain.

705,838 3/54 Great Britain.

755,519 3/54 Great Britain.

736,792 9/55 Great Britain.

775,308 5/57 Great Britain.

785,222 10/57 Great Britain.

826,689 1/60 Great Britain.

846,505 8/60 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

ABRAHAM H. WINKELSTEIN, Examiner.

1. IN THE PROCESS OF COLOURING CELLULOSE MATERIALS COMPRISING TREATMENTWITH A REACTIVE DYE-STUFF, THEREAFTER APPLYING A RESIN-FINISHING AGENTAND THEREAFTER BAKING THE TREATED MATERIAL TO CURE THE RESIN, THEIMPROVEMENT WHICH CONSISTS IN ADDING TO THE AQUEOUS LIQUOR CONTAININGTHE RESIN-FINISHING AGENT, AN ORGANIC CATIONIC DYE-FIXING AGENT FREEFROM ANIONIC SOLUBILIZING GROUPS AND HAVING AT LEAST ONE AMMONIUM GROUP.